Way to Enforce Selectivity via Steric Hindrance: Improvement of Am(III)/Eu(III) Solvent Extraction by Loaded Diphosphonic Acid Esters

Abstract

Hybrid donor extractants are a promising class of compounds for the separation of trivalent actinides and lanthanides. Here, we investigated a series of sterically loaded diphosphonate ligands based on bipyridine (BiPy-PO-iPr and BiPy-PO-cHex) and phenanthroline (Phen-PO-iPr and Phen-PO-cHex). We studied their complex formation with nitrates of trivalent f-elements in solvent extraction systems (Am and Eu) and homogeneous acetonitrile solutions (Nd, Eu, and Lu). Phenanthroline extractants demonstrated the highest efficiency and selectivity [<i>SF</i>(Am/Eu) up to 14] toward Am(III) extraction from nitric acid solutions among all of the studied diphosphonates of N-heterocycles. The binding constants established by UV-vis titration also indicated stronger binding of sterically impaired diphosphonates compared to the primary substituted diphosphonates. NMR titration and slope analysis during solvent extraction showed the formation of 2:1 complexes at high concentrations (>10^-3 mol/L) for phenanthroline-based ligands. According to UV-vis titrations at low concentrations (10^-5-10^-6 mol/L), the phenanthroline-based ligands formed 1:1 complexes. Bipyridine-based ligands formed 1:1 complexes regardless of the ligand concentration. Luminescence titrations revealed that the quantum yields of the complexes with Eu(III) were 81 ± 8% (BiPy-PO-iPr) and 93 ± 9% (Phen-PO-iPr). Single crystals of the structures [Lu(μ²,κ⁴-(iPrO)₂P(O)Phen(O)₂(OiPr))(NO₃)₂]₂ and Eu(Phen-PO-iPr)(NO₃)₃ were obtained by chemical synthesis with the Phen-PO-iPr ligand. X-ray diffraction studies revealed a closer contact of the <i>f</i>-element with the aromatic N atoms in the case of sterically loaded P═O ligands compared with sterically deficient ligands. Density functional theory calculations allowed us to rationalize the observed selectivity trends in terms of the bond length, Mayer bond order, and preorganization energy.